WO2018107572A1

WO2018107572A1 - Textile water-repellent finishing liquid based on fluorine-containing polyurethane, preparation method therefor, and use thereof

Info

Publication number: WO2018107572A1
Application number: PCT/CN2017/073014
Authority: WO
Inventors: 李战雄; 陈蕾; 遇娜; 刘群
Original assignee: 南通纺织丝绸产业技术研究院
Priority date: 2016-12-15
Filing date: 2017-02-06
Publication date: 2018-06-21
Also published as: CN106832194B; CN106832194A

Abstract

Disclosed in the present invention is a textile water-repellent finishing liquid based on fluorine-containing polyurethane, a preparation method therefor, and a use thereof. The preparation method comprises: adding a non-ionic surfactant and a cationic surfactant into a de-ionized water, slowly adding dropwise a fluoroalkyl-containing polyurethane solution, and further stirring at a high speed to obtain a uniform finishing liquid; and carrying out an addition polymerization reaction on the fluoroalkyl-containing polyurethane with fluoroalkyl-containing copolyether glycol and diisocyanate in the presence of a fluorine-containing solubilizing agent. Due to the structure of a fluoroalkyl lateral-group type polyether block, the fluorine-containing polyurethane has high fluorine content, and thus surface energy is low. The polyurethane is emulsified to prepare the finishing liquid which is used for finishing the textile and has a water contact angle of greater than 139.5 degrees; and the finishing liquid has excellent water-repellent function.

Description

Textile water-repellent finishing liquid based on fluorine-containing polyurethane and preparation method and application thereof

[0001] The present invention relates to a polyurethane finishing liquid, and in particular to a textile water-repellent finishing liquid based on a fluorine-containing polyurethane, a preparation method and application thereof, and belongs to the field of polyurethane polymers and textile finishing assistants.

Background technique

[0002] The surface free energy (γ _ε ) of a polymer solid is related to the element of its surface composition. The introduction of fluorine atoms significantly reduces the surface free energy, and the more fluorine atoms are substituted, the more effective the effect of reducing the surface free energy. If a fluorine atom is introduced into the surface of the fabric fiber so that the fluorine atom on the surface of the fabric reaches a certain concentration, the critical surface tension of the fiber will be greatly reduced, and when the critical surface tension is reduced to the point where water and oil cannot spread by themselves, Produces water and oil repellency on the surface of the fabric. The fluorine-containing finishing agent confirms the application according to this principle. Most of the fabric waterproofing agents currently used are side chain fluoroalkyl type polyacrylates, because the fluorine-containing alkyl acrylate can be conveniently introduced into the pendant polymer base in the polymer molecular backbone by radical polymerization. .

technical problem

[0003] Although polyurethane materials have superior high and low temperature properties and mechanical properties than polyacrylates, it is not easy to introduce a fluoroalkyl group on the polyurethane side groups. It is known that the raw material for synthesizing polyurethane is a polymer type dihydric alcohol (or polyhydric alcohol) and a diisocyanate. Since the monomer of the synthetic polymer type diol lacks the fluoroalkylated product, it is difficult to obtain the pendant type fluoropolymer diol; the idea of fluoroalkylation of the polyurethane by the fluoroalkylation of the diisocyanate is also Problems, such as diisocyanate, due to the small molecular weight, it is difficult to introduce a large amount of fluoroalkyl groups on the polyurethane macromolecule even if it is fluoroalkylated.

Problem solution

Technical solution

[0004] An object of the present invention is to provide a textile refractory finishing liquid based on fluoropolyurethane and a preparation method thereof

, with excellent low surface energy and water repellency. [0005] The present invention discloses a preparation method of a fluoropolyurethane-based textile water repellent finishing liquid, comprising the steps of adding a nonionic surfactant and a cationic surfactant to deionized water, and then adding fluorine The alkyl polyurethane solution is stirred to obtain a fluoropolyurethane-based textile water repellent finishing liquid; the chemical structure of the fluorine-containing polyurethane is:

[0006]

Wherein w is 2~7; m is 3 100; n is 1 100; x is 1~50; y is 1~20;

R is -(CH ₂ ) ₆ - or -Ph(CH ₃ )-; R' is -(CH ₂ ) ₄ -.

[0009] In the above aspect, under the action of a fluorine-containing solubilizing agent, a fluorine-containing polyurethane is obtained by addition polymerization of a fluorine-containing alkyl polyether glycol and a diisocyanate. The method comprises the following steps: mixing a ketone solvent and a fluorine-containing solubilizing agent, adding a fluorine-containing alkyl copolyether glycol, dibutyltin dilaurate; and then adding a diisocyanate dropwise at 40 to 65 ° C, the reaction is 1 to 12 small吋; then add 1,4-butanediol, continue to react 1~12 hours,

[0010] In the above technical solution, the ketone solvent is any one of acetone, butanone or cyclohexanone; the fluorine-containing solubilizing agent is trifluorotoluene and 1,3-bis(trifluoromethyl) Any one of benzene; the diisocyanate is any one of toluene diisocyanate (TDI) and hexamethylene diisocyanate (HDI).

[0011] In the above technical solution, the mass ratio of the ketone solvent, the fluorine-containing solubilizing agent, the fluorine-containing alkyl copolyether glycol, the dibutyltin dilaurate, the diisocyanate, and the 1,4-butanediol is (10~) 50) : (10~30) : (10-5 0) : (0.2~1) : (5~30) : (0.4~3).

[0012] In the above technical solution, the dices of the diisocyanate are added dropwise for 15 minutes to 1 hour.

[0013] In the above aspect, the fluorine-containing alkyl copolyether glycol is obtained by polymerizing a fluorine-containing oxetane and a fluorine-containing epoxy monomer. Adding a chlorinated alkane solvent and a starter to the reactor; then adding boron trifluoride diethyl ether at 0 to 10 ° C; then adding a fluorine-containing oxetane and a fluorine-containing epoxy monomer dropwise to carry out hydrazine Ring polymerization to obtain a fluorine-containing alkyl copolyether glycol; the initiator is ethylene glycol, 1,4-butanediol, 1,6-hexanediol Any of them.

[0014] In the above technical solution, mixing allyl acetate, sodium hydrogencarbonate, sodium dithionite, organic solvent, water, and then adding fluoroalkyl iodide at -20~5 ° C, the synthesis reaction, Then, the alkali solution is added dropwise to carry out a cyclization reaction to prepare a fluorine-containing epoxy monomer; mixed with butyl acetate, sodium hydrogencarbonate, sodium dithionite, an organic solvent, and water, and then dropped at -20 to 5 ° C. The perfluoroalkyl iodide is added to carry out a synthesis reaction, and then an alkali solution is added to carry out a cyclization reaction to obtain a fluorine-containing oxetane.

[0015] In the above technical solution, the perfluoroalkyl iodide is any one of heptafluoroiodopropane, nonafluoroiodobutane, tridecafluoroiodane, pentafluoroiodoheptane, and heptafluoroiodooctane. The organic solvent is hydrazine, hydrazine-dimethylformamide; the lye solution is any one of NaOH aqueous solution and KOH aqueous solution; the chlorinated alkane solvent is dichloromethane and dichloroethane. Any one of chloroform and carbon tetrachloride.

[0016] In the technical solution of the present invention, the preparation of the fluorine-containing polyurethane is carried out by addition polymerization of a fluorine-containing alkyl copolyether glycol and a diisocyanate, and catalyzed by a tin catalyst, and chain-extended by 1,4-butanediol. The reaction formula is as follows:

[0017] In the above technical solution, the nonionic surfactant is AEO-6; the cationic surfactant is octadecyltrimethylammonium bromide or octadecyltrimethylammonium chloride; The solvent in the fluorine-containing alkyl polyurethane solution is a ketone solvent/fluorine-containing solubilizing agent mixture; the fluorine-containing solubilizing agent is any one of trifluorotoluene and 1,3-bis(trifluoromethyl)benzene; The amount of the fluorine-containing alkyl polyurethane solution added dropwise was 10 to 20 minutes.

[0018] In the above technical solution, the mass ratio of the nonionic surfactant, the cationic surfactant, the deionized water, and the fluorine-containing alkyl polyurethane solution is (1.5 to 2): (1.5 to 2): (100 to 120) : (25 to 32); The fluoroalkyl polyurethane solution has a mass concentration of 60 to 75%.

[0019] The present invention also discloses a fluoropolyethylene-based textile water repellent finishing liquid prepared according to the above-mentioned preparation method of a fluoropolyethylene-based textile water repellent finishing liquid and its application in water repellent finishing of textiles.

[0020] The present invention further discloses a method for water repellent finishing of textiles, comprising the steps of: adjusting a solid content of a fluoropolyurethane-based textile water repellent finishing liquid to 40 g/L; and then subjecting the textile to wetting, padding, The pre-baking and baking process is carried out by water repellent finishing.

[0021] The present invention comprises a polyurethane prepolymer by addition polymerization of a fluorine-containing alkyl copolyether glycol and a diisocyanate, and the residual isocyanate group contained in the prepolymer and the chain extender 1,4-butanediol are chain extended. The reaction produces a fluorine-containing polyurethane and is emulsified to obtain a finishing liquid. The structure of the outermost surface layer of the fluoropolymer covering the substrate provides the outermost layer composition mainly of fluorine-containing groups; the pendant fluorine-containing alkyl polymer can be provided by surface enrichment of the side chain fluoroalkyl group More superior low surface energy.

Advantageous effects of the invention

Beneficial effect

[0022] The advantages of the invention are:

[0023] 1. The present invention uses a fluorine-containing alkyl copolyether glycol to synthesize a polyurethane. The fluorine-containing polyurethane has a pendant fluoroalkyl structure, and the product has a high fluorine content, and can provide excellent low surface energy for fabric finishing and water repellent. Excellent performance; the obtained polyurethane is used for fabric finishing, the water contact angle is higher than 139.5°, and has excellent water repellency;

[0024] 2. The invention improves the compatibility of the fluorine-containing alkyl copolyether glycol with the diisocyanate by adding a fluorine-containing solubilizing agent, and solves the prior art addition reaction with the diisocyanate due to the fluorine-containing polyether oleophobic oil. The difficult problem is that the addition polymerization reaction of the fluorine-containing alkyl polyether glycol and the diisocyanate is improved, and the addition reaction proceeds smoothly, thereby obtaining a polyurethane having uniform dispersion and good fluidity;

[0025] 3. The fluorine-containing polyurethane of the present invention has a fluoroalkyl group on a macromolecular side group and a high fluorine content. Therefore, it has excellent low surface energy; and the synthetic fluorine-containing polyurethane raw material is easy to obtain, the reaction condition is mild, the process is simple, and the industrial production is easy.

Brief description of the drawing

DRAWINGS

1 is an infrared spectrum diagram of a fluorine-containing polyurethane film prepared in Example 1;

2 is a water contact angle test chart of the fluorine-containing polyurethane finished cotton fabric prepared in Example 1;

3 is a water contact angle test chart of the fluorine-containing polyurethane finished cotton fabric prepared in Example 2;

4 is a water contact angle test chart of the fluorine-containing polyurethane finished cotton fabric prepared in Example 3;

5 is a water contact angle test chart of the fluoropolyurethane finished cotton fabric prepared in Example 4. [0030] FIG.

Embodiments of the invention

[0031] The technical solutions of the present invention are further described below in conjunction with the embodiments and the accompanying drawings.

Embodiment 1

(1) Synthesis of a fluorine-containing alkyl epoxy monomer

[0034] a synthesis of nonafluorooxetane

[0035] In a 1000 mL three-necked flask equipped with a thermometer, ice water bath and magnetic stirrer, 16.5 g of butyl acetate, 26.6 g of sodium hydrogencarbonate (NaHC0 ₃ ), 55.0 g of sodium dithionite, 220 g of N, N were added. - dimethylformamide, 210 g of water, 55.4 g of perfluorobutyl iodide was added dropwise, reacted at -15 ° C for 3 h, slowly warmed to room temperature, and kept at room temperature for 2 h. After completion of the reaction, extraction was carried out three times with 150 g of toluene. The combined extracts were washed with water three times to obtain a 4-nonafluorobutyl-3-iodobutyl acetate solution, which was added to a 1000 mL three-necked flask, and 305 g of a 20% by mass sodium hydroxide solution was added dropwise. The reaction was kept at 15 ° C for 3 h. After the reaction, the layers were separated. The organic layer was washed with water three times, dried and evaporated under reduced pressure to give 3,3 g of 3-(indole, succinyl-nonafluoropentyl) oxetane in a yield of 75.9.

[0036] b. nonafluoropropylene oxide synthesis

[0037] In a 1000 mL three-necked flask equipped with a thermometer, ice water bath and magnetic stirrer, 14.2 g of allyl acetate, 26.6 g of sodium bicarbonate, 55.0 g of sodium dithionite, 220 g were added.

Ν, Ν-dimethylformamide, 210 g of water, 55.4 g of perfluorobutyl iodide was added dropwise, reacted at -20 ° C for 4 h, slowly warmed to room temperature, and kept at 4 h. After completion of the reaction, extraction was carried out in three portions of 180 g of trifluorotoluene. Combined extract, water After washing 4 times, a 3-nonafluorobutyl-2-iodopropyl acetate solution was prepared, which was directly added to a 1000 mL three-necked flask, and 533 g of a 10% by mass sodium hydroxide solution was added dropwise thereto, and the solution was kept at 12 °C reaction lh. After the reaction, the layers were separated. The organic layer was washed with water three times, and the solvent was evaporated to dryness, and the solvent was evaporated to give hexane, succinyl-nonafluoropentyl propylene oxide (33. 9 g, yield: 80.3 < 3⁄4).

(2) Synthesis of fluorine-containing alkyl polyether

[0039] a mixed monomer

27.8 g of 3-(anthracene, fluorenyl-nonafluoropentyl)oxetane and 26.4 g of hydrazine, fluorene-nonafluoropentyl propylene oxide were uniformly mixed to obtain a mixed monomer.

[0041] b. copolymerization

[0042] In a three-necked flask equipped with a thermometer, a stirrer and a constant pressure dropping funnel, under nitrogen protection, adding 50 g of dichloromethane and 0.32 g of 4-butanediol, and cooling to 2 ° C in an ice water bath. Slowly add 0.1 lgBF ₃ .Et ₂ 0 , the temperature is raised by about 3 ° C, and after reacting for 30 minutes, the prepared mixed monomer is added dropwise, and the addition is completed in 35 minutes. After the addition was completed, the temperature was raised to 30 ° C, and the reaction was continued for 24 hours. Stop the reaction.

[0043] c post processing

[0044] The above-mentioned anthracene ring copolymerization reaction solution was added with 10 g of a solution of 2.5<3⁄4 NaHCO^J, and the reaction was terminated. After stirring for 1 hour, the mixture was extracted three times with 120 g of dichloromethane, and the organic layer was combined and dried over anhydrous magnesium sulfate. After 1 hour, the desiccant was removed by filtration, and the filtrate was evaporated to give 49.3 g of product (yield: 91.2%).

(3) Polyurethane Synthesis

[0046] In a 500 ml three-necked flask equipped with a magnetic stirrer, a thermometer, a reflux condenser, and a N ₂ protective device, 35 g of methyl ethyl ketone, 15 g of benzotrifluoride, and 38 g of a fluorine-containing alkyl copolyether glycol were added, and stirred and dissolved. Then, 0.5 g of dibutyltin dilaurate (DBTL) was added, and after heating to 55 ° C, 14.9 g of hexamethylene diisocyanate (HDI) was added dropwise, and the addition was completed for 30 minutes. After the addition, the reaction was carried out at 55 ° C for 6 hours. After the viscosity of the reaction solution was increased, l.lg,4-butanediol was added. After the reaction was continued for 3 hours, most of the solvent was distilled off under reduced pressure, and butanone was added while hot. /Trifluorotoluene (volume ratio 1:1) The solvent was mixed, and the product was diluted to a weight of 82.5 g, a mass concentration of about 65%, and cooled to give a fluorine-containing alkyl polyurethane solution. After the product was formed into a film, the infrared spectrum of the test was as shown in Fig. 1. FT-IR (KBr tablet): 1717.6 cm ^{1 was} assigned to the amide I bond and the ester group (C=0), and 1538.3 cm ^{-1 was} assigned to the amide bond (NH). Deformation vibration), 1127.6 cm -1 is attributed to the CF characteristic absorption peak. The resulting polyurethane has the following structural formula. LJ

Wherein m is 3 to 10; n is 2 to 10; x is 3 to 30; y is 3 to 20;

[0048] (4) Organizing the application

[0049] a. emulsification treatment

[0050] 1.8 g of a nonionic surfactant AEO-6 and 1.8 g of a cationic surfactant octadecyltrimethylammonium bromide were added to 110 parts of deionized water in a high-profile beaker and stirred to dissolve. The high-speed shearing at 8000 rpm was carried out, and 31.2 g of a fluorine-containing alkyl polyurethane solution was slowly added dropwise, and the addition was completed in 15 minutes. After the addition, the mixture was further stirred at high speed for 15 minutes to obtain a uniform emulsion.

[0051] b. fabric finishing

[0052] The obtained fluorine-containing polyurethane is diluted to 40g / L, applied to cotton fabric finishing, the process flow is: infiltration (30 min, bath ratio 1:20) → two dip two rolling (rolling rate 100%, room temperature) → Prebaking (90 ° C x 3 min) → baking (160 ° C x 3 min).

(5) Contact angle test

[0054] The contact angle of the cotton fabric test to water was measured. The test results are shown in Fig. 2, and the contact angle was 139.5.

Example 2

(1) Synthesis of a fluorine-containing alkyl epoxy monomer

[0057] a synthesis of nonafluoro oxetane

[0058] In a 1000 mL three-necked flask equipped with a thermometer, ice water bath and magnetic stirrer, 16.8 g of butyl acetate, 27.2 g of sodium hydrogencarbonate (NaHC0 ₃ ), 55.6 g of sodium dithionite, 225 g of N, N were added. - dimethylformamide, 200 g of water, 55.8 g of perfluorobutyl iodide was added dropwise, reacted at -13 ° C for 3 h, slowly warmed to room temperature, and kept at 4 h. After completion of the reaction, extraction was carried out three times with 160 g of toluene. The combined extracts were washed with water three times to obtain a 4-nonafluorobutyl-3-iodobutyl acetate solution, which was added to a 1000 mL three-necked flask, and 312 g of a 15% by mass sodium hydroxide solution was added dropwise. The reaction was kept at 12 ° C for 4 h. After the reaction, the layers were separated. The organic layer was washed with water three times, dried and evaporated under reduced pressure to give 3,3 g of 3-(indole, yttrium-nonafluoropentyl) oxetane in a yield of 77.4 %. [0059] b. nonafluoropropylene oxide synthesis

[0060] In a 1000 mL three-necked flask equipped with a thermometer, ice water bath and magnetic stirrer, 14.3 g of allyl acetate, 26.8 g of sodium hydrogencarbonate, 54.8 g of sodium dithionite, 218 g were added.

Ν, Ν-dimethylformamide, 206 g of water, 55.9 g of perfluorobutyl iodide was added dropwise, reacted at -19 ° C for 4 h, slowly warmed to room temperature, and kept at 4 h. After completion of the reaction, extraction was carried out in 3 portions with 185 g of trifluorotoluene. The combined extracts were washed with water 4 times to obtain 3-nonafluorobutyl-2-iodopropyl acetate solution, which was directly added to a 1000 mL three-necked flask, and 425 g of a 15% by mass sodium hydroxide solution was added dropwise. , heat preservation at 12 ° C for 2h. After the reaction is completed, the layers are separated. The organic layer was washed with water three times, and the solvent was evaporated.

(2) Synthesis of fluorine-containing alkyl polyether

[0062] a mixed monomer

21.3 g of 3-(anthracene, fluorenyl-nonafluoropentyl)oxetane and 32.6 g of hydrazine, fluorene-nonafluoropentyl propylene oxide were uniformly mixed to obtain a mixed monomer.

[0064] b. copolymerization

[0065] In a three-necked flask equipped with a thermometer, a stirrer and a constant pressure dropping funnel, under nitrogen protection, adding 62 g of dichloromethane and 0.40 gl, 4-butanediol, and cooling to 2 ° C in an ice water bath. 0.15 g of BF ₃ .Et ₂ 0 was slowly added, the temperature was raised by about 3 ° C, and after reacting for 50 minutes, the prepared mixed monomer was added dropwise, and the addition was completed in 35 minutes. After the addition was completed, the temperature was raised to 30 ° C, and the reaction was continued for 36 hours. Stop the reaction.

[0066] c post processing

[0067] The above-mentioned anthracene ring copolymerization reaction solution was added with 10 g of 2.5 <3⁄4 NaHCO ^ solution, the reaction was terminated, and the reaction was stirred for 1 hour, and then extracted with 120 g of dichloromethane for 3 times. The organic layer was combined and dried over anhydrous magnesium sulfate. After the desiccant was removed by filtration, the filtrate was evaporated to give 48.1 g of product, yield: 89.2%.

(3) Polyurethane Synthesis

[0069] In a 500 ml three-necked flask equipped with a magnetic stirrer, a thermometer, a reflux condenser, and a N ₂ protective device, 32 g of methyl ethyl ketone, 18 g of benzotrifluoride, and 40 g of a fluorine-containing alkyl copolyether glycol were added. After stirring and dissolving, 0.5 g of dibutyltin dilaurate (DBTL) was added, and after heating to 60 ° C, 15.6 g of hexamethylene diisocyanate (HDI) was added dropwise, and the addition was completed for 30 minutes. After the addition, the reaction was carried out at 55 ° C for 6 hours. After the viscosity of the reaction solution was increased, 1.5 g of 4-butanediol was added, and after the reaction was continued for 3 hours, most of the solvent was distilled off under reduced pressure. The solvent was mixed with methyl ethyl ketone/trifluorotoluene (1:1 by volume), and the product was diluted to a weight of 80 g and a mass concentration of 69.5%. The effluent was cooled to give a fluorine-containing alkyl polyurethane solution. Among them, the polyurethane structural formula is as follows.

Wherein m is 3 to 8; n is 5 to 20; x is 3 to 30; y is 3 to 20;

[0071] (4) Organizing the application

[0072] a. emulsification treatment

[0073] 2.0 g of a nonionic surfactant AEO-6 and 1.8 g of a cationic surfactant octadecyltrimethylammonium chloride were added to 108 parts of deionized water in a high-profile beaker and stirred to dissolve. The high-speed shearing at 8000 rpm was carried out, and 30.1 g of a fluorine-containing alkyl polyurethane solution was slowly added dropwise, and the addition was completed in 15 minutes. After the addition, the mixture was further stirred at a high speed for 15 minutes to obtain a uniform emulsion.

[0074] b. fabric finishing

[0075] The obtained fluorine-containing polyurethane is diluted to 40g / L, applied to cotton fabric finishing, the process flow is: infiltration (3 Omin, bath ratio 1:20) → two dip two rolling (rolling rate 100%, room temperature) → Pre-bake (90 ° C x 3 min) → Baking (160 ° C x 3 min).

(5) Contact angle test

[0077] The cotton fabric was tested for contact angle with water. The test results are shown in Fig. 3, and the contact angle was 141.7.

Example 3

(1) Synthesis of a fluorine-containing alkyl epoxy monomer

a. Trifluorotrioxetane synthesis

[0081] In a 1000 mL three-necked flask equipped with a thermometer, ice water bath and magnetic stirrer, 16.8 g of butyl acetate, 27.9 g of sodium hydrogencarbonate, 54.8 g of sodium dithionite, 235 g were added.

Ν, Ν-dimethylformamide, 230 g of water, 72.6 g of perfluorohexyl iodane was added dropwise, reacted at -14 ° C for 5 h, slowly warmed to room temperature, and kept at room temperature for 6 h. After completion of the reaction, extraction was carried out in 3 portions with 188 g of trifluorotoluene. The combined extracts were washed with water three times to prepare a 4-trifluorohexyl-3-iodobutyl acetate solution, which was directly added to a 1000 mL three-necked flask, and 51 lg of 10% by weight sodium hydroxide was added dropwise. The solution was incubated at 15 ° C for 6 h. End of reaction After layering. The organic layer was washed with water three times, dried and evaporated under reduced pressure to give <RTI ID=0.0>>

[0082] b. Trifluoropropylene oxide synthesis

[0083] In a 1000 mL three-necked flask equipped with a thermometer, ice water bath and magnetic stirrer, 14.7 g of allyl acetate, 27. lg sodium bicarbonate, 55.4 g of sodium dithionite, 226 g were added.

Ν, Ν-dimethylformamide, 215 g of water, 73.9 g of perfluorohexyl iodane was added dropwise, reacted at -16 ° C for 4 h, slowly warmed to room temperature, and kept at a reaction time for 6 h. After completion of the reaction, extraction was carried out in three portions of 190 g of trifluorotoluene. The combined extracts were washed with water three times to obtain a 3-trifluorohexyl-2-iodopropyl acetate solution, which was directly added to a 1000 mL three-necked flask, and 522 g of a 10% by mass sodium hydroxide solution was added dropwise. , heat preservation at 20 ° C for 4h. After the reaction is completed, the layers are separated. The organic layer was washed with water three times, dried and evaporated under reduced pressure to give yt, yt-trifluoroheptyl propylene oxide 41. 3 g, yield 70.9%.

(2) Synthesis of fluorine-containing alkyl polyether

[0085] a. anthracene ring copolymerization

25.2 g of 3-(anthracene, fluoren-decafluoroheptyl)oxetane and 48.1 g of hydrazine, decane-tridecafluoroheptylcyclopropane were uniformly mixed to obtain a mixed monomer.

[0087] In a three-necked flask equipped with a thermometer, a stirrer and a constant pressure dropping funnel, added under nitrogen, 60 g of dichloromethane and 0.52 g of 4-butanediol were added, and the temperature was lowered to 2 ° C in an ice water bath. 0.8 g of BF ₃ .Et ₂ 0 was slowly added, the temperature was raised by about 5 ° C, and after reacting for 50 minutes, the above-mentioned prepared mixed monomer was added dropwise, and 1 hour of addition was completed. After the addition was completed, the temperature was raised to 28 ° C and the reaction was continued for 24 hours. Stop the reaction.

[0088] b. Post processing

[0089] The above anthracene ring polymerization reaction solution was added with 16 g of 2.5<3⁄4 Na ₂ CO ^ solution, the reaction was terminated, and the reaction was stirred for 2 hours, and then extracted with 186 g of dichloromethane for 3 times, the organic layer was combined, and desiccant anhydrous sodium sulfate was added thereto. After drying for 1 hour, the desiccant was removed by filtration, and the filtrate was evaporated to give a product (yield: 65.2 g).

(3) Polyurethane Synthesis

[0091] In 500ml three-necked flask equipped with a magnetic stirrer, thermometer, reflux condenser and N ₂ protection device, the acetone was added 37g, 18g trifluorotoluene, fluorinated alkyl co-added 32g polyether diol, stirred to dissolve, Then, 0.5 g of dibutyltin dilaurate (DBTL) was added, and after heating to 55 ° C, 11.2 g of toluene diisocyanate (TDI) was added dropwise, and the addition was completed for 35 minutes. After the addition, the reaction was carried out at 55 ° C for 5 hours, and the viscosity of the reaction solution was increased, and then added. L.lg l,4-butanediol, after continuing to react for 3 hours, most of the solvent is distilled off under reduced pressure at 65 ° C and 20 mmHg, and acetone/trifluorotoluene (1:1 by volume) mixed solvent is added while hot. The product was diluted to a weight of 67. 5 g, and the mass concentration was about 66%, and the mixture was cooled to obtain a fluorine-containing alkyl polyurethane solution. Among them, the polyurethane structural formula is as follows.

Wherein m is 3 to 10; n is 3 to 20; x is 5 to 30; y is 5 to 20;

[0093] (4) Organizing the application

[0094] a. emulsification treatment

[0095] In a high-profile beaker, 1.9 g of a nonionic surfactant AEO-6 and 1.8 g of a cationic surfactant octadecyltrimethylammonium chloride were added to 100 parts of deionized water, and dissolved by stirring. High-speed shearing at 8000 rpm, 26.5 g of fluoroalkyl polyurethane solution was added dropwise, and the addition was completed in 15 minutes. After the addition, stirring was continued for 15 minutes at high speed to obtain a uniform emulsion.

[0096] b. fabric finishing

[0097] The obtained fluorine-containing polyurethane is diluted to 40g / L, applied to cotton fabric finishing, the process flow is: infiltration (3 Omin, bath ratio 1:20) → two dip two rolling (rolling rate 100%, room temperature) → Pre-bake (90 ° C x 3 min) → Baking (160 ° C x 3 min).

(5) Contact angle test

[0099] The contact angle of the cotton fabric test to water was measured. The test results are shown in Fig. 4, and the contact angle was 143.8°.

Example 4

(1) Synthesis of fluorine-containing alkyl epoxy monomer

a. Trifluorooxetane synthesis

[0103] In a 1000 mL three-necked flask equipped with a thermometer, ice water bath and magnetic stirrer, 16.9 g of butyl acetate, 28. g of sodium hydrogencarbonate, 55.3 g of sodium dithionite, 241 g were added.

Ν, Ν-dimethylformamide, 225 g of water, 73.2 g of perfluorohexyl iodane was added dropwise, reacted at -13 ° C for 6 h, slowly warmed to room temperature, and kept at a temperature of 3 h. After completion of the reaction, extraction was carried out in three portions of 180 g of trifluorotoluene. Combined extract, water After washing 3 times, a 4-trifluorohexyl-3-iodobutyl acetate solution was prepared, which was directly added to a 1000 mL three-necked flask, and 510 g of a 10% by mass sodium hydroxide solution was added dropwise thereto, and the solution was kept at 15 °C reaction for 6h. After the reaction, the layers were separated. The organic layer was washed with water three times, dried and evaporated under reduced pressure to give <RTI ID=0.0>>

b. Synthesis of trifluoropropylene oxide

[0105] In a 1000 mL three-necked flask equipped with a thermometer, ice water bath and magnetic stirrer, 14.5 g of allyl acetate, 27.0 g of sodium hydrogencarbonate, 55.1 g of sodium dithionite, 219 g were added.

Ν, Ν-dimethylformamide, 220 g of water, 73.4 g of perfluorohexyl iodane was added dropwise, reacted at -15 ° C for 4 h, slowly warmed to room temperature, and kept at a reaction time for 6 h. After completion of the reaction, extraction was carried out in three portions of 185 g of trifluorotoluene. The combined extracts were washed with water three times to prepare a 3-trifluorohexyl-2-iodopropyl acetate solution, which was directly added to a 1000 mL three-necked flask, and 520 g of a 10% by mass sodium hydroxide solution was added dropwise. , heat preservation at 20 ° C for 6h. After the reaction is completed, the layers are separated. The organic layer was washed with water for 4 times, dried and evaporated under reduced pressure to give yt, yt-trifluoroheptyl propylene oxide 39. 8 g, yield 68.4 <3⁄4.

(2) Synthesis of fluorine-containing alkyl polyether

a. anthracene ring copolymerization

36.4 g of 3-(anthracene, fluoren-decafluoroheptyl)oxetane and 28.9 g of hydrazine, decane-tridecafluoroheptylcyclopropane were uniformly mixed to obtain a mixed monomer.

[0109] In a three-necked flask equipped with a thermometer, a stirrer and a constant pressure dropping funnel, under nitrogen protection, adding 55 g of dichloromethane and 0.45 g of 4-butanediol, and cooling to 2 ° C in an ice water bath. 0.6 g of BF ₃ .Et ₂ 0 was slowly added, the temperature was raised by about 4 ° C, and after reacting for 45 minutes, the above-mentioned prepared mixed monomer was added dropwise, and 1 hour of addition was completed. After the addition was completed, the temperature was raised to 25 ° C and the reaction was continued for 24 hours. Stop the reaction.

[0110] b. Post processing

[0111] The above anthracene ring polymerization reaction solution was added to 12 g of 2.5<3⁄4 Na ₂ CO solution, and the reaction was terminated. After stirring for 2 hours, the mixture was extracted three times with 165 g of dichloromethane, and the organic layer was combined and dried over anhydrous sodium sulfate. After 1 hour, the desiccant was removed by filtration, and the filtrate was evaporated to give 51.1 g of product, yield 78.6%.

(3) Polyurethane Synthesis

[0113] In a 500 ml three-necked flask equipped with a magnetic stirrer, a thermometer, a reflux condenser, and a N ₂ protective device, 35 g of acetone, 20 g of benzotrifluoride, and 28 g of a fluorine-containing alkyl copolyether glycol were added, and stirred and dissolved. Then 0.4 g of dibutyltin dilaurate (DBTL) was added, and after heating to 55 ° C, 9.5 g of toluene diisocyanate (TDI) was added dropwise, and the addition was completed for 35 minutes. After the addition, the reaction was carried out at 55 ° C for 5 hours. After the viscosity of the reaction solution was increased, 1.0 g of 4-butanediol was added thereto, and the reaction was continued for 3 hours. Then, most of the solvent was distilled off under reduced pressure, and acetone/trifluorobenzene was added while hot. Toluene (volume ratio 1:1) mixed solvent, the product was diluted to a weight of 56.5 g, the mass concentration was about 68.

1%, cooled to produce a fluorine-containing alkyl polyurethane solution. Among them, the polyurethane structural formula is as follows.

Wherein m is 3 to 10; n is 2 to 10; x is 5 to 30; y is 5 to 20;

[0115] (4) Organizing the application

[0116] a. emulsification treatment

[0117] 1.5 g of a nonionic surfactant AEO-6 and 1.6 g of a cationic surfactant octadecyltrimethylammonium bromide were added to 100 parts of deionized water in a high-profile beaker, and stirred to dissolve. The high-speed shearing at 8000 rpm was carried out, and 25.3 g of a fluorine-containing alkyl polyurethane solution was slowly added dropwise, and the addition was completed in 15 minutes. After the addition, the mixture was further stirred at a high speed for 15 minutes to obtain a uniform emulsion.

[0118] b. Fabric finishing

[0119] The obtained fluorine-containing polyurethane was diluted to 40 g / L, applied to cotton fabric finishing, the process flow is: infiltration (3 Omin, bath ratio 1:20) → two dip two rolling (rolling rate 100%, room temperature) → Pre-bake (90 ° C x 3 min) → Baking (160 ° C x 3 min).

(5) Contact angle test

[0121] The contact angle of the cotton fabric test to water was measured. The test results are shown in Fig. 5, and the contact angle was 144.6.

Claims

Claim

[Claim 1] A method for preparing a fluoropolyethylene-based textile water repellent finishing liquid, comprising the steps of: adding a nonionic surfactant and a cationic surfactant to deionized water, and then adding the The fluoroalkyl polyurethane solution is stirred to obtain a fluoropolyurethane-based textile water repellent finishing liquid; the chemical structural formula of the fluoropolyurethane is:

Where w is 2~7; m is 3 100; n is 1 100; x is 1~50; y is 1~20;

R is -(CH ₂ ) ₆ - or - Ph(CH ₃ )-; R' is -(CH ₂ ) ₄ -.

[Claim 2] The method for preparing a fluorine-containing polyurethane-based textile water repellent finishing liquid according to claim

The method comprises the following steps: mixing a ketone solvent and a fluorine-containing solubilizing agent, adding a fluorine-containing alkyl copolyether glycol, and dibutyltin dilaurate; and then adding a diisocyanate dropwise at 40 to 65 ° C. The reaction is carried out for 1 to 12 hours; then, 1,4-butanediol is added, and the reaction is continued for 1 to 12 hours to obtain a fluorine-containing alkylpolyurethane.

[Claim 3] The method for preparing a fluoropolyurethane-based textile water repellent finishing liquid according to claim 2

, the ketone solvent is any one of acetone, butanone or cyclohexanone; the fluorine-containing solubilizing agent is in trifluorotoluene and 1,3-bis(trifluoromethyl)benzene Any one of; the diisocyanate is any one of toluene diisocyanate (TDI) and hexamethylene diisocyanate (HDI); a ketone solvent, a fluorine-containing solubilizer, a fluorine-containing alkyl copolyether glycol, The mass ratio of dibutyltin dilaurate, diisocyanate, and 1,4-butanediol is (10~5 0): (10~30) : (10~50) : (0.2~1) : (5~30) : (0.4~3); Add diisocyanate to the crucible for 15 minutes ~ 1 hour.

[Claim 4] The method for preparing a fluoropolyethylene-based textile water repellent finishing liquid according to claim 3

, characterized in that: a chlorinated alkane solvent and an initiator are added to the reactor; and then at 0 to 10. Add boron trifluoride diethyl ether under C; then add fluorinated oxetane and fluorine-containing epoxy The oxime ring polymerization is carried out to obtain a fluorine-containing alkyl copolyether diol; the initiator is any one of ethylene glycol, 1,4-butanediol, and 1,6-hexanediol; Mixing allyl acetate, sodium hydrogencarbonate, sodium dithionite, organic solvent, water, then adding perfluoroalkyl iodide at -20~5 ° C, synthesizing the reaction, then adding the lye to the ring a reaction, preparing a fluorine-containing epoxy monomer; mixing vinyl acetate, sodium hydrogencarbonate, sodium dithionite, an organic solvent, and water, and then adding a perfluoroalkyl iodide at -20 to 5 ° C, The synthesis reaction is carried out, followed by addition of a lye to carry out a cyclization reaction to obtain a fluorine-containing oxetane.

[Claim 5] The method for preparing a fluoropolyethylene-based textile water repellent finishing liquid according to claim 4

And the perfluoroalkyl iodide is any one of heptafluoroiodopropane, nonafluoroiodobutane, tridecafluoroiodane, pentafluoroiodoheptane, and heptafluorooctyl iodide; The organic solvent is hydrazine, hydrazine-dimethylformamide; the lye solution is any one of NaOH aqueous solution and KOH aqueous solution; the chlorinated alkane solvent is dichloromethane, dichloroethane, trichloro Any of methane and carbon tetrachloride.

[Claim 6] The method for preparing a fluoropolyurethane-based textile water repellent finishing liquid according to claim

Is characterized in that: the nonionic surfactant is AEO-6; the cationic surfactant is octadecyltrimethylammonium bromide or octadecyltrimethylammonium chloride; The solvent in the alkyl polyurethane solution is a ketone solvent/fluorine-containing solubilizing agent mixture; the fluorine-containing solubilizing agent is any one of trifluorotoluene and 1,3-bis(trifluoromethyl)benzene; The fluoroalkyl polyurethane solution has a turn of 10 to 20 minutes.

[Claim 7] The method for preparing a fluoropolyethylene-based textile water repellent finishing liquid according to claim

, characterized in that the mass ratio of the nonionic surfactant, the cationic surfactant, the deionized water, and the fluorine-containing alkyl polyurethane solution is (1.5 to 2): (1.5 to 2): (100 to 120): (25 ~32); The fluoroalkyl polyurethane solution has a mass concentration of 60 to 75%.

[Claim 8] A fluoropolyethylene-based textile water repellent finishing liquid prepared by the method for preparing a fluoropolyethylene-based textile water repellent finishing liquid according to any one of claims 1 to 7.

[Claim 9] A method for water repellent finishing of textiles, comprising the steps of: adjusting the solid content of the fluoropolyethylene-based textile water repellent finishing liquid of claim 8 to 40 g/L; The process of wetting, padding, pre-baking, and baking is carried out by water repellent finishing. [Claim 10] The use of the fluoropolyethylene-based textile water repellent finishing liquid according to claim 8 in textile water repellent finishing.